Thermoplastic resin composition

ABSTRACT

A thermoplastic resin composition comprising a blend obtainable by blending 0.1 to 99 % by weight of (a) a fluorine-containing polymer having a number-average molecular weight of 2000 to 1000000 and having hydroxy group or epoxy group at least at one of end portions of a main chain and side chain of the polymer, and 1 to 99.9 % by weight of (b) a heat resisting thermoplastic resin having a crystalline melting point or glass transition temperature of not less than 150° C. The present invention can provide a composition comprising various heat resisting thermoplastic resins and a fluorine-containing polymer having a functional group which is capable of developing an affinity with said resins and forming a uniform dispersion.

TECHNICAL FIELD

[0001] The present invention relates to a thermoplastic resincomposition which comprises a specific fluorine-containing polymerhaving a functional group and a thermoplastic resin having a crystallinemelting point or glass transition temperature of not less than 150° C.,and has improved mechanical and chemical properties.

BACKGROUND ARTS

[0002] Heat resisting crystalline thermoplastic resins (having acrystalline melting point of not less than 150° C.) such as polyacetals,polyamides, aromatic polyesters, polyallylene-sulfides, polyketones,polyether ketones, polyamide imides and polyether nitrites are excellentin mechanical properties and moreover moldability, and therefore areused for functional parts for automobiles, industrial machineries,office automation equipments, and electrical and electronic equipments.Meanwhile there is a market demand for higher chemical resistance,sliding properties and the like, and particularly impact resistance isdesired to be enhanced because those resins are generally brittle. Also,heat resisting amorphous thermoplastic resins (having a glass transitiontemperature of hot less than 150° C.) such as polycarbonates,polyphenylene ethers, polyalylates, polysulphones, polyether sulphones,and polyetherimides are widely used for making the best use oftransparency, dimensional stability, impact resistance, and the like,but generally there are problems with chemical resistance, solventresistance and moldability.

[0003] Fluorine-containing resins such as polytetrafluoroethylene(PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA),tetrafluoroethylene/hexafluoropropylene copolymer (FEP), polyvinylidenefluoride (PVDF) and ethylene/tetrafluoroethylene copolymer (ETFE) areexcellent in thermal resistance, chemical resistance, solventresistance, weather resistance, sliding properties, pliability,electrical properties and the like, and are widely used for automobiles,industrial machineries, office automation equipments, electrical andelectronic equipments, and the like. However, there are many cases wherethose resins are inferior in mechanical properties and physical thermalresistance as represented by a deflection temperature under load, ascompared with heat resisting crystalline thermoplastic resins, and theuses thereof are within the limited range because the dimensionalstability is inferior as compared with heat resisting amorphousthermoplastic resins.

[0004] Attempts have been actively made to obtain novel materials bycombining a fluorine-containing polymer (including resinous andelastomeric form) with the aforementioned heat resisting thermoplasticresins having no fluorine to modify such resins to eliminatedisadvantages of the resins, and on the contrary by combining mainly aresinous fluorine-containing polymer with the heat resistingthermoplastic resin having no fluorine to moldify such polymers.

[0005] First, as an example for simply melting and blending by the useof a kneading machine, JP-A-202344/1982 discloses that afluorine-containing elastomer commercially available is added to improveimpact resistance, crack resistance and strength against thermal shockwithout imparing properties of polyallylene sulfides such as thermalresistance, chemical resistance, and the like. Also, JP-A-165647/1989and JP-A-110156/1990 disclose that a polymer, that is to say, a liquidcrystal polymer (aromatic polyester or the like) forming an anisotropicmelt is added to decrease a coefficient of linear expansion withoutimpairing weather resistance, chemical resistance, wear resistance andanti-soil property of a fluorine-containing polymer such as a PVDF andfurther to improve mechanical properties and moldability. As examples ofa blend of a liquid crystal polymer and a PTFE, there are JP-B-5693/1992and JP-A-230756/1988. JP-A-7850/1975 discloses that it is effective toblend the PVDF for improving water absorption and hygroscopicity ofpolyamides.

[0006] Furthermore, JP-A-23448/1985 discloses an example that a propertyof release from a mold is improved by blending a fluorine-containingpolymer with an aromatic polysulphone composition of which shrinkagefrom mold dimensions has been decreased by blending fibrousreinforcements such as glass fiber and wollastonite and inorganicfillers such as talc and glass beads.

[0007] Also, attempts have been widely and generally made to improvesliding properties of various synthetic resins by blending a PTFEpowder.

[0008] However, since a surface energy of a fluorine-containing polymeris small, there is a problem that such a polymer is generally short ofan affinity with other materials. Therefore, when thefluorine-containing polymer and other materials are melted and blended,there occurs a phase separation. Interfacial adhesion thereof is nearlynothing substantially, and an interfacial adhesive failure occurseasily, the fluorine-containing polymer is difficult to be dispersed inother materials during blending, and an aggregation occurs. Thus it isdifficult to display an effect of blending that polymer.

[0009] In order to eliminate such drawbacks and to enhance an affinitybetween different polymers, it is often conducted to add so-calledcompatibilizing agents as the third component. JP-A-218446/1987discloses a composition prepared by blending a thermoplasticfluorine-containing elastomer to improve impact resistance ofpolyallylene sulfides without imparing flowability thereof, and thatpatent publication describes that it is more effective to add afluoroaliphatic group-containing polymer to improve an affinity of thepolymer. Also, JP-A-62853/1988 discloses a method to add, as acompatibilizing agent, a graft polymer comprising a vinyl polymer havingepoxy group and a methyl methacrylate polymer or anacrylonitrile/styrene copolymer when blending polyallylene sulfides andthermoplastic resins containing a PVDF.

[0010] Also, claim 2 of the mentioned JP-A-165647/1986, JP-A-197551/1986and JP-A-263144/1986 disclose that it is more effective to add anacrylic polymer, polyvinyl acetate and polyvinyl methyl ketone,respectively than a simple blending, in blending a PVDF and a polymerforming an anisotropic melt.

[0011] JP-A-11109/1989 discloses an example of using, as acompatibilizing agent for blending polyamides and PVDF, a block polymercomprising any one of N-vinylpyrrolidone or methyl(meta)acrylate and anyone of unsaturated ethylenic monomer, polycondensated monomer or lactam.

[0012] Also, JP-A-98650/1986 and JP-A-110550/1986 disclose that whenblending a polyphenylene ether and a fluorine-containing polymer like aPVDF, a copolymer comprising polystyrene and an acrylic polymer is usedas a compatibilizing agent, taking advantage of an excellentcompatibility of polyphenylene ether with polystyrene and PVDF withacrylic polymer.

[0013] However, in JP-A-218446/1987, an effect of an improvement inaffinity property is insufficient. It may be because a fluoroaliphaticgroup in an compatibilizing agent is of low polymerization having carbonatoms of not less than 20. All the other publications substantiallydescribes the examples of using compatibilizing agents having nofluorine, which are synthesized, making use of an excellent affinitybetween a PVDF and a carbonyl group-containing polymer such as acrylicpolymer, and the fluorine-containing polymer is limited to the PVDF. Inthe method to improve an affinity by the use of such a compatibilizingagent, there is a problem that physical properties of the moldedarticles deteriorate because chemical resistance and thermal resistanceof the compatibilizing agents themselves are inferior to that of a maincomponent, i.e. the polymer.

[0014] Also, attempts have been made to improve dispersibility of acomposition comprising a fluorine-containing polymer and a thermoplasticresin, by a so-called dynamic vulcanization. JP-A-185042/1991 disclosesthat, when blending a crosslinkable fluorine-containing elastomer and athermoplastic polymer having a crystalline melting point or glasstransition temperature of not less than 150° C., the dispersibility isenhanced and a thermoplastic elastomer can be obtained by vulcanizingthe fluorine-containing elastomer during melting and blending.JP-A-172352/1991 also discloses that a fine dispersion of afluorine-containing rubber is achieved by improving impact resistance ofa polyphenylene sulfide by the use of a fluorine-containing elastomer byutilizing the dynamic vulcanization method.

[0015] Though those dynamic vulcanization methods are economicallyadvantageous since the vulcanization of the fluorine-containingelastomer is carried out during melting and blending with othermaterials, there is a problem that impurities resulting from vulcanizingagents and other additives, which are used in the usual vulcanizationmethods, remain in a composition, and properties such as chemicalresistance of a molded article deteriorate.

[0016] On the other hand, there are reports on a composition using afluorine-containing polymer having a reactive functional group.JP-A-105062/1988, JP-A-254155/1988 and JP-A-264672/1988 discloseexamples of blending a matrix polymer and, for instance, afluoropolyether in which a functional group is introduced at the endthereof, a polymer containing a functional group and a polyfluoroalkylgroup having carbon atoms of 2 to 20 and a fluorine-containing elastomerhaving a functional group. However, any of those examples is a manner toform, a network structure by dispersing the polymer having two kinds offunctional groups in the matrix polymer and causing an inter-reactiontherebetween and to physically bond that network structure to the matrixpolymer, but not a manner to directly utilize a chemical affinity andreactivity with the matrix polymer.

[0017] Thus a combination of functional groups of not less than twokinds reacting with each other is necessary without fail, and also it isnecessary to provide the conditions for forming the network structure bythose functional groups. Also, a fluoropolyether is usually obtained asan oily substance and is expensive, and an effect of addition thereof isonly limited to an improvement of lubricity of the matrix polymer.Furthermore exemplified is only such a polyfluoroalkyl group-containingpolymer of a low molecular weight which is difficult to be prescribed asa polymer.

[0018] As mentioned hereinabove, when blending a fluorine-containingpolymer and a thermoplastic resin, it is difficult to obtain a blendhaving stable characteristics because the fluorine-containing polymer isgenerally short of an affinity, and physical properties of the moldedarticle obtained using that polymer are deteriorated. In order toimprove the affinity, various studies have been made in relation toadditives, but the present status is such that a composition comprisinga fluorine-containing polymer and a thermoplastic resin, which do notdeteriorate thermal resistance, chemical resistance and the like of thecomposition, has not yet been obtained.

[0019] The object of the present invention is to provide a compositioncomprising various heat resisting thermoplastic resins andfluorine-containing polymers having a functional group, which have agood affinity with the resins and are capable of forming uniformdispersing conditions.

DISCLOSURE OF THE INVENTION

[0020] The thermoplastic resin composition of the present inventioncomprises a blend obtainable by blending (a) 0.1 to 99% (% by weight,hereinafter the same) of a fluorine-containing polymer having afunctional group and (b) 1 to 99.9% of a heat resisting thermoplasticresin having a crystalline melting point or glass transition temperatureof not less than 150° C.; said fluorine-containing polymer (a) havingthe functional group is at least one selected from fluorine-containingpolymers having functional groups, in which a concentration of thefunctional groups at the end portion of a main chain and the side chainportion is 2 to 2000 μmol/g per the total weight of thefluorine-containing polymer, represented by the formula [I],

A¹XYA²  [I]

[0021] wherein X is a structural unit of the formula —CH₂CX¹X²(wherein X¹ and X² are the same or different, and each is hydrogen atom,fluorine atom, CH₂_(p)O_(q)R—B¹ (R is a dihydric hydrocarbon grouphaving carbon atoms of 1 to 20 or dihydric fluorine-substituted organicgroup having carbon atoms of 1 to 20, B¹ is hydrogen atom, fluorineatom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1),—OCO—R—B¹ (R and B¹ are the same as above) or —COO—R—B¹ (R and B¹ arethe same as above));

[0022] Y is a structural unit of the formula CF₂CY¹Y² (wherein Y¹ andY² are the same or different, and each is hydrogen atom, fluorine atom,chlorine atom, CF₂_(r)O_(s)R_(f)_(t)CH₂_(u)B² (R_(f) is adihydric fluorine-substituted organic group having carbon atoms of 1 to14, B² is hydrogen atom, halogen atom, hydroxy group, epoxy group orglycidyloxy group, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is aninteger of 1 to 3) or CF₂_(v)B³ (B³ is hydrogen atom, fluorine atom orchlorine atom, v is an integer of 1 to 10));

[0023] both A¹ and A² are end portions of a main chain; provided thateach of X and Y may comprise two or more structural units;

[0024] Y may not be present when X has the structural unit derived fromCH₂═CHF, CH₂═CF₂ or fluoroalkyl-α-substituted acrylate (substituent ishydrogen atom, fluorine atom or methyl);

[0025] X may not be present when Y has the structural unit derived fromCF₂═CF₂ or CF₂═CFCl;

[0026] at least one of A¹ and A² contains hydroxy group, epoxy group orglycidyl group when both of X and Y do not contain hydroxy group, epoxygroup or glycidyl group.

BRIEF EXPLANATION OF THE DRAWINGS

[0027]FIG. 1 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 2.

[0028]FIG. 2 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 3.

[0029]FIG. 3 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 1.

[0030]FIG. 4 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 2.

[0031]FIG. 5 is a stress-strain curve of the molded article obtained inExamples 6 to 8 and Comparative Examples 3 and 4.

[0032]FIG. 6 is a microscopic photograph of a cut surface of the moldedarticle obtained in Example 12.

[0033]FIG. 7 is a microscopic photograph of a cut surface of the moldedarticle obtained in Comparative Example 9.

PREFERRED EMBODIMENTS OF THE INVENTION

[0034] Though a prior resin composition of a heat resistingthermoplastic resin and a fluorine-containing polymer could provide auniform molded article only by a special method, according to thepresent invention, there can be provided a composition capable of easilymaking a uniform molded article by introducing a specific functionalgroup into a fluorine-containing polymer.

[0035] The fluorine-containing polymer having a functional group isrepresented by the formula (I), and is characterized in that the polymerhas hydroxy group or epoxy group (inclusive of a glycidyl group) atleast at one of end portions of a main chain and end portions of sidechains if present, and the fluorine-containing polymer (I) or aprecursor polymer before introducing a functional group to obtain (I) isprepared by a radical polymerization. The details are mentionedhereinbelow.

[0036] The fluorine-containing polymer having a functional group of thepresent invention has basic structural units of X represented byCH₂—CX¹X² and Y represented by CF₂—CY¹Y².

[0037] As monomers producing the structural unit X, there are employed,for instance, olefins such as ethylene, propylene, 1-butane andisobutylene; for instance, fluoroalkenes such as CH₂═CHF, CH₂═CF₂,CH₂═C(CF₃)₂ and CH₂═CZ(CF₂)wZ (z is hydrogen atom or fluorine atom and wis an integer of 1 to 8. For instance, CH₂═CHCF₂CF₂CF₂CF₃,CH₂═CHCF₂CF₂CF₂CF₂CF₂CF₃, CH₂═CFCF₃, CH₂═CFCF₂CF₃, CH₂═CFCF₂CF₂CF₂H andCH₂═CFCF₂CF₂CF₂CF₂CF₂H); alkylvinylethers, for instance, CH₂═CHOCH₂CH₃,CH₂═CHOCH₂CH₂CH₂CH₃ and

[0038] fluoroalkyl vinylethers, for instance, CH₂═CHOCH₂CF₂CF₂H,CH₂═CHOCH₂CF₂CF₂CF₂CF₂H and CH₂═CHOCH₂CH₂CF₂CF₂CF₂CF₂CF₂CF₃;hydroxyalkyl vinylethers, for instance, CH₂═CHOCH₂CH₂ CH₂CH₂OH;fluoroalkyl allylethers, for instance, CH₂═CHCH₂OCH₂CH₂CF₂CF₃;hydroxyalkyl allylethers, for instance, CH₂═CHCH₂OCH₂CH₂OH; alkyl orallylvinyl esters, for instance, CH₂═CHOCOCH₃, CH₂═CHOCOC(CH₃)₃ and

[0039] alkyl-α-substituted acrylates, of which substituent is hydrogenatom, fluorine atom or methyl, for instance, CH₂═CHCOOCH₃,CH₂═C(CH₃)COOCH₃ and CH₂═CFCOOCH₃; fluoroalkyl-α-substituted acrylates,of which substituent is hydrogen atom, fluorine atom or methyl, forinstance, CH₂═CHCOOCH₂CF₂CF₂CF₃, CH₂═C(CH₃—)COOCH₂CF₂CF₃,CH₂═C(CH₃)COOCH₂CF₂CF₂H and CH₂═CFCOOCH₂CF₂CF₃;hydroxy(fluoro)alkyl-α-substituted acrylates, of which substituent ishydrogen atom, fluorine atom or methyl, for instance, CH₂═CHCOOCH₂CH₂OH,CH₂═C(CH₃)COOCH₂CH₂OH and CH₂═C(CH₃)COOCH₂CF₂CF₂CH₂OH;CH₂═CHCH₂C(CF₃)20H; CH₂═CHCH₂OH;

[0040] As monomers producing the structural unit Y, there are employed,for instance, fluoroalkenes such as CF₂═CFH, CF₂═CF₂, CF₂═CFC1,CF₂═CZ(CF₂)_(w)Z (Z and w are the same as those mentioned hereinbefore,for instance, CF₂═CHCF₃, CF₂═CFCF₃, CF₂═CFCF₂CF₃ and CF₂═CFCF₂CF₂H);formulae, for instance, CF₂═CFCH₂CH₂OH, CF₂═CFCF₂CH₂OH,CF₂═CFCF₂CF₂CH₂CH₂OH and

[0041] a compound represented by CF₂═CF—R_(f)CH₂_(x)B² (R_(f) and B₂are the same as mentioned hereinabove, and x is an integer of 1 to 3);perfluoro(alkylvinyl ether), for instance, CF₂═CFOCF₃,CF₂═CFO(CF₂CF(CF₃)O)_(y)CF₂CF₂CF₃ (y is an integer of 1 to 3), andCF₂═CFOCF₂CF₂CF₂CF₃; formulae, for instance, CF₂═CFOCF₂CF₂CH₂OH,CF₂═CFOCF₂CF₂CF₂CH₂OH, CF₂═CFOCF₂CF(CF₃)OCF₂CF₂CF₂CH₂OH,CF₂═CFOCF₂CF₂CH₂ Br, CF₂═CFOCF₂CF₂CH₂OCF₂CF₂CH₂F, CF₂═CFOCF₂CF₂ CH₂I andCF₂═CFOCF₂CF(CF₃)OCF₂CF₂CH₂I: a compound represented byCF₂═CF—O—R_(f)CH₂_(z)B² (R_(f) and B² are the same as mentionedhereinabove, and z is an integer of 1 to 3); perfluoro(alkylallylether),for instance, CF₂═CFCF₂OCF₂CF₂CF₃.

[0042] The structural units X and Y each may comprise two kinds or moreof structural units, Y may not be present, when X has the structuralunit derived from CH₂═CHF, CH₂═CF₂ or fluoroalkyl-α-substitutedacrylates (A substituent is hydrogen atom, fluorine atom or methyl). Xmay not be present, when Y has the structural unit derived from CF₂═CF₂or CF₂═CFC1.

[0043] A¹ and A² representing the end portions of a main chain-X—Y— arecut pieces of an initiator or a chain transfer agent, for instance,—OCOR¹, —OR¹, —R¹, COOH, hydrogen atom, halogen atom (R¹ is an alkylgroup or fluoroalkyl group having carbon atoms of 1 to 10), but notlimited to those. When any of structural units X and Y does not includea structural unit having hydroxy group, epoxy group or glycidyl group,at least one of A¹ and A² must include hydroxy group, epoxy group orglycidyl group.

[0044] A basic component of a fluorine-containing polymer (a) having afunctional group has the structure represented by the formula (I), andis formed by a radical polymerization. As is explicit from the formula(I), the polymer does not have an ether bond at a portion of the mainchain. A fluorine-containing polymer having an ether bond at the bondedportion of the main chain, for instance, a perfluoroxy alkylene unit isalso disclosed in JP-B-42446/1991 besides the JP-A-105062/1988,JP-A-254155/1988 and JP-A-264672/1988. That fluoropolyether is usuallymade by an ion polymerization, and is expensive. Furthermore, thefluoropolyether of a high molecular weight is difficult to be obtained.The fluoropolyether becomes in the form of grease or oil at roomtemperature or at a high temperature, and it is difficult to form auniform blend of fluoropolyether alone with a thermoplastic resin, whichresults in deterioration of physical properties of the obtained blend.Also, it is difficult to introduce a side chain into thefluoropolyether.

[0045] A functional group (hydroxy group or epoxy group (Glycidyl groupis also included therein hereinafter the same)) in thefluorine-containing polymer represented by the formula (I) can be madealso by using the mentioned functional group-containing monomer, andalso can be introduced, for example, by the method mentioned below.

[0046] For instance, there is a method (method with an initiator) topolymerize a basic component by the use of an initiator for the radicalpolymerization, which has a functional group to be introduced. Whenusing, for instance, a hydroperoxide as an initiator, hydroxy group canbe introduced at the end of the main chain.

[0047] Also, a functional group can be introduced by the use of aspecific chain transfer agents (method with a chain transfer agent).Hydroxy group is introduced at the end of the main chain when, forinstance, methanol and mercaptoethanol are used as a chain transferagent.

[0048] Also, another preferable method is the one (polymer reactionmethod) to introduce a functional group at the end or side chain of apolymer by a polymer reaction after polymerization. The polymer reactionmethod includes a polymerization using a radical polymerizationinitiator, which can easily convert a cut piece of the initiator at theend of the polymer into an intended functional group afterpolymerization and, in the same manner, a polymerization using a chaintransfer agent and comonomer, which can easily convert the ends of amain chain and side chain of the polymer into an intended functionalgroup after polymerization.

[0049] As a polymer reaction method, there is an example, for instance,to convert, into an intended functional group, iodine at the end of apolymer polymerized by using, as a chain transfer agent, an iodinatedcompound containing an iodine, such as a fluorine-containing elastomerand a thermoplastic fluorine-containing elastomer. Concretely, suitableis a fluorine-containing elastomer disclosed in JP-A-40543/1977, whichis mainly comprises a copolymer comprising a VDF and at least one kindof the other fluorine-containing monomers which are copolymerizable withthe VDF, wherein 0.001 to 10% by weight, preferably 0.01 to 5% by weightof iodine is bonded at the end of a polymer chain, and a thermoplasticfluorine-containing elastomer disclosed in JP-B-4728/1982, which has atleast one block of fluorine-containing resin as a hard segment and atleast one block of fluorine-containing elastomer as a soft segment,wherein the thermoplastic fluorine-containing elastomer is a linear,branched or radial block copolymer having a weight ratio offluorine-containing resin to fluorine-containing elastomer of 5:95 to60:40. An iodine of a fluorine-containing polymer, of which end isiodinated, has much reactivity and can be converted to a functionalgroup such as epoxy group, hydroxy group, carboxyl group, amino group-and isocyanate group by the known organic chemical method. The end ofthe polymer becomes an epoxy group after addition of an allylalcohol andthen dehydroiodination by an alkali, or becomes hydroxy group by addingethylene and further reacting with dimethyl sulfoxide.

[0050] Also, as disclosed in JP-A-12734/1987, a side chain typefluorine-containing polymer having a functional group can be made byletting a halogen be contained in the side chain by copolymerizing 0.05to 20% by mole of a halogen-containing monomer among those representedby the formula of CF₂═CFOCF₂CFR²O_(a)CF₂CF₂CH₂O_(b)CF₂CF₂—CH₂—R³(wherein R² is F or CF₃, a is an integer of 0 to 2, b is an integer of 0to 2 and R³ is a halogen atom), in which R³ is selected from Cl, Br andI, and 80 to 99.95% by mole of a monomer producing a structural unit Xand a structural unit Y if necessary, and then by converting to afunctional group in the same manner as the example of the iodineterminated fluorine-containing polymer.

[0051] As a method to introduce a functional group by using a polymerreaction, there can be adopted, for instance, as shown in Polym. Mater.Sci Eng., 49,518 (1983), such a method as to add a nucleophilicfunctional group into a double bond produced by dehydrofluorinating afluorine-containing elastomer having vinyliden fluoride with a base.However, that method has a drawback that the functional group isdifficult to be quantitatively introduced.

[0052] It is naturally possible to further convert thefluorine-containing polymer having a functional group which isintroduced by each of the mentioned methods, to the polymer having thedesired functional group by applying the usual organic chemicaltechnique to the polymer reaction. For instance, the iodine at the endand/or side chain of the fluorine-containing polymer can also beconverted to glycidyloxy group by converting the iodine of the polymerto hydroxy group and further reacting with an epichlorohydrin.

[0053] Also, it is possible to combine the functional group introducingmethods such as the method with an initiator, method with a chaintransfer agent, copolymerization method and polymer reaction method. Thereaction for introducing a functional group can also be carried out in amelting and kneading equipment such as an extruder, and not limited toin a polymerization reactor for a general use.

[0054] In the formula (I), such a polymer as containing CH₂ unit in amain chain in combination of X and Y as mentioned below is preferablebecause a wide range of temperature for kneading with a thermoplasticresin can be selected and a compatibility with the thermoplastic resinis relatively excellent among fluorine-containing polymers.

[0055] That is to say, one (referred to as Polymer P¹) is a polymerusing CH₂═CF₂ (vinylidene fluoride: VDF) as at least one component of Xin the formula (I) (others are the same as those of the formula (I)),and another one (referred to as Polymer P²) is a copolymer containing atleast one of hydrocarbon olefins as X (VDF is not contained) and atleast one of CF₂═CF₂ (tetrafluoroethylene: TFE), CF₂═CFC1(chlorotrifluoroethylene: CTFE) or CF₂═CFCF₃ (hexafluoropropene: HFP) asY (others are the same as those of the formula (I)). Any of thosepolymers has hydroxy group or epoxy group at least at one of the mainchain and the end of the side chain thereof.

[0056] Among those polymers having CH₂ unit at the main chain, furtherpreferable is the one which is excellent in a thermal stability (thermalresistance), when kneaded with a thermoplastic resin. The main chain andthe end of the side chain, which have a functional group, are usuallyinferior to the other parts in thermal resistance, and it is unavoidableeven if there is a thermal decomposition to a certain extent on kneadingas far as an effect thereof can be recognized. However, at least mainportions of the main chain and the side chain of the aforesaidfluorine-containing polymer having a functional group should havethermal resistance of 170° C. at lowest, preferably not less than 250°C. The thermal resistance depends mainly on a kind and ratio ofcomponents of the monomers to be used. In the Polymer P¹ and Polymer P²,when a hydrocarbon olefin is used as X, it is recommendable to lower aratio of the hydrocarbon olefins such as alkylvinyl ether and alkylvinylester excluding CH₂═CH₂, CH₂═CHCH₃ and CH₂═C(CH₃)₂ in the polymer to notmore than 20% by mole. This is because those may be thermally the mostunstable portions, among the monomers producing the fluorine-containingpolymer having a functional group of the present invention.

[0057] The thermal resistance of the present invention means atemperature at the time of weight decrease by 1% in a measurement(raising at a rate of 10° C./minute) of a thermobalance in a nitrogengas stream.

[0058] Among the Polymer P¹ and Polymer P², there are employed belowparticularly preferable fluorine-containing polymers having a functionalgroup in order to further give the features such as oil resistance andchemical resistance, which are inherent to fluorine-containing polymers,to the composition, even if the thermal resistance is enough asmentioned hereinabove.

[0059] That is to say, the Polymer P¹ essentially comprises apolyvinylidene fluoride (PVDF) and VDF, and is obtained bycopolymerization with at least one selected from, for instance, TFE,CTFE, perfluoro(alkylvinyl ether), perfluoro(alkylallyl ether),CH₂═C(CF₃)₂, CF₂═CZ(CF₂)_(w)Z (Z and w are the same as mentionedhereinabove), CH₂═CZ(CF₂)_(w)Z (Z and w are the same as mentionedhereinabove), CF₂═CFR_(f)(CH₂)_(z)—B₂ and fluorine-containing olefinssuch as fluoroalkene represented by CF₂═CFOR_(f)(CH₂)_(z)—B² (R_(f), B²,x and z are the same as mentioned hereinabove), and occasionallyfurthermore with at least one hydrocarbon olefin selected from CH₂═CH₂,CH₂═CHCH₃ and CH₂═C(CH₃)₂, wherein at least one end of the main chainand the side chains of the polymer has hydroxy group or epoxy group.

[0060] The Polymer P² is a polymer containing at least one hydrocarbonolefin selected from CH₂═CH₂, CH₂═CHCH₃ and CH₂═C(CH₃)₂, at least one ofTFE, CTFE, and CF₂═CFCF₃ (hexafluoropropene: HFP), and occasionally,further at least one fluorine-containing olefin selected from, forinstance, perfluoro(alkylvinyl ether), perfluoro(alkylallyl ether),CH₂═C(CF₃)₂, CF₂═CZ(CF₂)_(w)Z (Z and w are the same as mentionedhereinabove), CH₂═CZ(CF₂)_(w)Z (Z and w are the same as mentionedhereinabove), fluoroalkylvinylether, CF₂═CFR_(f)(CH₂)_(x)—B² andfluoroalkene represented by CF₂═CFOR_(f)(CH₂)_(z)—B² (R_(f), B², x and zare the same as mentioned hereinabove), wherein at least one end of themain chain and the side chains of the polymer has hydroxy group or epoxygroup.

[0061] A molecular weight of the fluorine-containing polymer having afunctional group of the present invention is the same level as those ofa usual fluorine-containing resin and fluorine-containing elastomerexcept a PTFE which is said to have a high molecular weight of usuallynot less than millions, and is 2000 to 1000000 in a number-averagemolecular weight. When the molecular weight is too low, thermalresistance and chemical resistance are impaired, and therefore, it isnecessary to decrease a content of a fluorine-containing polymer havinga functional group in the composition When the molecular weight is toohigh, moldability is impaired. Preferable number-average molecularweight differs depending on a kind of a thermoplastic resin and apurpose of the composition, but is about 10000 to 500000. Aconcentration of functional groups in the fluorine-containing polymer ofthe present invention may be a minimum necessary for improving adispersion condition when blending with the thermoplastic resin. Whenthe functional group is only at the end of a molecule, the concentrationof the functional group is too low and the effect is insufficient unlessthe fluorine-containing polymer is of relatively low molecular weight.In case where a functional group is introduced at the side chain with afunctional group-containing comonomer or by a high polymer reaction, theconcentration of the functional group can be relatively freely selectedirrespective of a molecular weight. However, an excessive concentrationof the functional group is not desirable by the reason of a restrictionin the production and in view of properties such as thermal resistanceand chemical resistance of the composition. The concentration of thefunctional groups both at the ends and in side chains of the moleculecan be 2 to 2000 μmol/g, particularly preferably 2 to 1000μ mol/g perthe total weight of the fluorine-containing polymer.

[0062] The fluorine-containing polymer (a) having a functional group ofthe present invention may be in either resinous or elastomeric formdepending on a kind of a monomer to be used and a ratio of componentsthereof. The resin is discriminated from the elastomer in a point thatthe latter has a glass transition temperature lower than roomtemperature, and either one can be selected depending on the purpose ofa blend. The elastomeric fluorine-containing polymer having a functionalgroup is used for the purposes to improve impact resistance of thethermoplastic resin and to obtain a blend in the elastomeric form.

[0063] In the present invention, the fluorine-containing polymer (a)having a functional group is blended with a thermoplastic resin (b) of acrystalline melting point or a glass transition temperature of not lessthan 150° C. As the thermoplastic resin (b), there are, for example,polyacetals, polyamides, polycrbonates, polyphenylene ethers, aromaticpolyesters, aromatic polyesteramides, aromatic azomethines, polyallylenesulfides, polysulfones, polyether sulfones, polyketones, polyetherketones, polyetherimides, polyamide imides, polymethyl pentenes andpolyether nitrites. Among those, preferable for the present inventionare thermoplastic resins which have a high thermal resistance, and donot deteriorate thermal resistance of a composition after mixed with thefluorine-containing polymer (a) having a functional group, orthermoplastic resins, for which usual impact modifiers and chemicalresistance modifiers cannot be used because thermal resistance isdeteriorated thereby. Examples of such resins are aromatic polyesters,polyamides, polyamide imides, polyallylene sulfides, polyketones,polyether nitrites, polycarbonates, polyphenylene ethers, polysulfones,polyetherimides and polyimides.

[0064] Further, particularly preferable are, for example, polyallylenesulfides, of which impact resistance is generally desired to be improvedwithout impairing thermal resistance and chemical resistance, andpolyamides which are desired to improve solvent resistance, particularlygasohol resistance for the use as materials for auto parts and aromaticpolyesters which are expected to enhance moldability and mechanicalproperties of the fluorine-containing polymer, being added thereto.Among those, particularly preferable are liquid crystal polyestersforming an anisotropic melt, which can be expected to enhance, to alarge extent, mechanical properties, moldability, dimensional stabilityand deflection temperature under load by enhancing a compatibility withthe fluorine-containing polymer, because those polyesters have highmodulus of elasticity and are excellent in moldability and dimensionalstability.

[0065] Also, when considering reactivity of the fluorine-containingpolymer (a) having a functional group of the present invention and athermoplastic resin (b), since polyphenylene sulfides contain mercaptogroup, polyamides contain carboxyl group and amino group, and aromaticpolyesters contain hydroxy group, carboxyl group and ester group, thereis a high possibility of those resins' reacting with hydroxy group orepoxy group (also inclusive of glycidyl group) in thefluorine-containing polymer having a functional group of the presentinvention. From this point of view, too, those resins are preferable.

[0066] The functional group of the fluorine-containing polymer of thepresent invention are epoxy group (including glycidyl group) and hydroxygroup. The reactivity of those functional groups is high with an esterbond of a main chain and hydroxy group and carboxyl group at the endwhen the heat resisting thermoplastic resin (b) is an aromaticpolyester, with an amide bond of main chain and carboxyl group and aminogroup at the end when the resin is a polyamide (PA), and with mercaptogroup at the end when the resin is a polyallylene sulfide. That is tosay, it can be thought that those highly reactive functional groups areintroduced in the fluorine-containing polymer, and partly react with themain chain or the end of the thermoplastic resin to improve acompatibility of the polymer or that the introduction of the functionalgroup enhances a polarity of the fluorine-containing polymer, whichimproves an interface affinity with the thermoplastic resin and adispersibility without particularly causing a chemical reaction. Also,it can be considered that a part of the thermoplastic resin causes achemical reaction with the fluorine-containing polymer and the reactionproducts act as a compatibilizing agent.

[0067] Therefore, in the composition of the present invention, a blendof the fluorine-containing polymer (a) having the functional group andthe thermoplastic resin (b) is presumed to be present in the form of

[0068] (1) a mere mixture of the fluorine-containing polymer (a) havingthe functional group and the thermoplastic resin (b),

[0069] (2) a reaction product between the fluorine-containing polymer(a) having the functional group and the thermoplastic resin (b) or

[0070] (3) a mixture of (1) and (2).

[0071] Thus, though a mechanism of the blend is not clear, it does notlimit the present invention.

[0072] It is not excluded from the present invention that thethermoplastic resin (b) is modified by a normal method in order toenhance an affinity or reactivity with the fluorine-containing polymerhaving a functional group of the present invention.

[0073] The resin composition of the present invention can also containpolymer components other than the thermoplastic resin (b) and thefluorine-containing polymer (a) having a functional group.

[0074] Preferable components are fluorine-containing polymers which haveneither hydroxy group nor epoxy group at the main chain and the end ofthe side chain in the formula (I). Particularly preferable are

[0075] (1) a perfluoro fluorine-containing resin or elastomer such asPTFE (including a copolymer having less than 1% by weight offluorine-containing olefin copolymerable with TFE),TFE/perfluoro(alkylvinyl ether) copolymer (so-called PFA), TFE/HFPcopolymer (so-called FEP) and TFE/perfluoro(alkylvinyl ether)/HFPterpolymer;

[0076] (2) a resinous copolymer, in which a mole ratio of an ethylene toa TFE and/or CTFE, which are known as a so-called ETFE and ECTFE, is 2:3to 3:2 and the third fluorine-containing monomer copolymerable therewithis contained in an amount of 0 to 15% by mole per a total amount of theethylene and the TFE and/or CTFE monomer, or an elastomeric copolymerhaving about 40 to 90% by mole of ethylene, about 0.1 to 20% by mole ofTFE and/or CTFE and about 10 to 60% by mole of the thirdfluorine-containing monomer. As the third fluorine-containing monomer,there is used at least one of those represented by CH₂═CZ(CF₂)_(w)Z,CF₂═CZ(CF₂)_(w)Z, CF₂═CFO(CF₂)_(w)Z (Z and w are the same as mentionedhereinabove) and CH₂═C(CF₃)₂;

[0077] (3) a PVDF and a VDF copolymer (a resinous or elastomericcopolymer of the VDF and at least one fluorine-containing olefinselected from TFE, CTFE, HFP, CH₂═C(CF₃)₂, (CF₃)₂C═O, and the like),wherein VDF/HFP copolymer, VDF/CTFE copolymer and VDF/TFE/HFP or CTFEterpolymer usually become an elastomer in the range of about 20 to 80%by mole of VDF, less than about 40% by mole of TFE, about 10 to 60% bymole of HFP and about 15 to 40% by mole of CTFE; and

[0078] (4) other fluorine-containing resins or elastomers such aschlorotrifluoroethylene (PCTFE) and poly(fluoroalkyl-α-substitutedacrylate) (a substituent is hydrogen atom, a methyl, fluorine atom orchlorine atom).

[0079] That is to say, in the compositions having three components ofthe aforesaid fluorine-containing polymer (a) having a functional group,the thermoplastic resin (b) and the fluorine-containing polymer havingno functional group, it can be thought that a mixture of a part of thethermoplastic resin (b) in the composition and the fluorine-containingpolymer (a) having a functional group functions as a compatibilizingagent and enhances a dispersibility, and a mechanical property, chemicalresistance, and the like, which cannot be obtained in case of a simpleblend of a fluorine-containing polymer having no functional group and athermoplastic resin (b), can be enhanced.

[0080] Therefore, in those compositions, it is preferable that thefluorine-containing polymer (a) having a functional group and thefluorine-containing polymer having no functional group are highlycompatible with each other.

[0081] For example, when mixing the perfluoro fluorine-containing resinor elastomer of (1) above and the polymer of (2) above, such as a ETFEand ECTFE, with the thermoplastic resin, it is the most preferable tomix a fluorine-containing polymer having a functional group, which hasthe functional group at the end or the side chain and has a structuresimilar to those of fluorine-containing polymers to be mixed therewith.

[0082] Also, when mixing the PVdF or the VdF copolymer of (3) above withthe thermoplastic resin, it is the most preferable to mix thefluorine-containing polymer having a functional group, which is selectedfrom PVdF and VdF copolymers and has the functional group at the end orthe side chain thereof.

[0083] It is necessary to blend the thermoplastic resin (b) and thefluorine-containing polymer (a) having a functional group or to blendthose and a fluorine-containing polymer having no functional group undermelting and fluidizing conditions at least at not less than acrystalline melting point or a glass transition temperature of thethermoplastic resin. It is desirable that the fluorine-containingpolymer having a functional group is also under melting conditionsduring blending, but a non-melting property may be maintained because ofa high melting viscosity or a crosslinking property.

[0084] The resin composition of the present invention has the functionalgroup at the end of the main chain and/or the side chain, and isobtained by mixing a fluorine-containing polymer (a) having a molecularweight of 2000 to 1000000 and a thermoplastic resin (b) having acrystalline melting point or glass transition temperature of not lessthan 150° C. The polymer (a) is 0.1 to 99% by weight, and the resin (b)is 1 to 99.9% by weight.

[0085] When (a) is 0.1 to 40% by weight and (b) is 60 to 99.9% byweight, such properties as an impact resistance, sliding property,chemical resistance and moldability can be improved by afluorine-containing polymer, though those properties are drawbacks formany of thermoplastic resins. Also, when (a) is 40 to 99% by weight and(b) is 1 to 60% by weight, a strength, deflection temperature underload, moldability and dimensional stability of the fluorine-containingpolymer can be improved by the thermoplastic resin. When, in a weightratio to the resin composition, (a) is less than 0.1% by weight and (b)is less than 1% by weight, the effect of that improvement becomesunsatisfactory.

[0086] A content, in the composition, of a fluorine-containing polymerhaving a functional group and a kind thereof differ depending on a kind,position, concentration, basic component and molecular weight of thefunctional group, and therefore, cannot be determined unequivocally butis selected depending on a kind of thermoplastic resin to be blended inthe mentioned range and a purpose of blending.

[0087] The preferable resin composition of the present invention is thecomposition comprising a fluorine-containing polymer having hydroxygroup or epoxy group at the end of main chain or the side chain and apolyallylene sulfide, polyamide, aromatic polyester or polycarbonate.

[0088] A polyallylene sulfide is excellent in thermal resistance,chemical resistance, and mechanical properties, but inferior in impactresistance.

[0089] There can be obtained a composition, of which impact resistanceis improved by mixing a fluorine-containing elastomer particularlyhaving a number-average molecular weight of 2000 to 200000, amongfluorine-containing polymers (a) having a functional group.

[0090] As a functional group of the fluorine-containing elastomer havinga functional group, there are employed hydroxy group and epoxy group(including glycidyl group). Either of those groups enhances adispersibility and impact resistance.

[0091] A preferable concentration of the functional group differsdepending on a kind and mixing ratio of a fluorine-containing elastomerand a polyallylene sulfide, and 2 to 2000 μmol/g, particularly 2 to 1000μmol/g is sufficiently effective per a total amount of thefluorine-containing elastomer.

[0092] As the aforesaid fluorine-containing elastomers having afunctional group, there can be used those, in which the functionalgroups are introduced at the respective ends or side chains thereof,such as vinylidene fluoride-hexafluoropropylene copolymer, vinylidenefluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidenefluoride-chlorotrifluoroethylene copolymer,vinylidenefluoride-tetrafluoroethylene-chlorotrifluoroethylenecopolymer, propylenetetrafluoroethylene copolymer,tetrafluoroethyleneperfluoroalkyl vinyl ether copolymer,tetrafluoroethylenevinylidene fluoride-propylene copolymer,ethylenetetrafluoroethylene-hexafluoropropylene copolymer,ethylene-hexafluoropropylene copolymer, perfluoroalkyl acrylateelastomer, tetrafluoroethylene-alkylvinylether copolymer, andtetrafluoroethylene-alkylvinylester copolymer. Among those, particularlypreferable are vinylidene fluoride-hexafluoropropylene copolymer,vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymerand propylene-tetrafluoroethylene copolymer, in which hydroxy group orepoxy group (including glycidyl group) is introduced respectively.

[0093] The fluorine-containing elastomer having a functional group andthe polyallylene sulfide can be used in the range of 0.1 to 40% byweight and 60 to 99.9% by weight, respectively, particularly preferably5 to 30% by weight and 70 to 90% by weight, respectively.

[0094] When the fluorine-containing elastomer having a functional groupis less than 5% by weight, impact resistance cannot be improvedsufficiently, and contrarily when exceeding 30% by weight, mechanicalstrength decreases remarkably.

[0095] Perfluoro fluorine-containing resins (PTFE, FEP, PFA, and thelike), ETFE, ECTFE, PVdF and VDF copolymer resins are excellent inthermal resistance, chemical resistance, weather resistance, electricalproperties, and the like, but there are many cases where those resinsare inferior to the heat resisting crystalline thermoplastic resin (b)in mechanical properties and physical thermal resistance as representedby a deflection temperature under load.

[0096] The mechanical property and deflection temperature under load,which fluorine-containing resins themselves have, can be improved,instead of using the aforesaid fluorine-containing resins, by blendingan aromatic polyester or polycarbonate with the fluorine-containingresin having a functional group of the present invention, which isintroduced at the end or the side chain thereof, or by using, as acompatibilizing agent, the fluorine-containing polymer having afunctional group of the present invention, for the mentioned blend ofthe fluorine-containing resin and the aromatic polyester orpolycarbonate.

[0097] When blending with the aromatic polyester or polycarbonate, theboth of hydroxy group and epoxy group (including glycidyl group) of thepresent invention can be used as the functional group of thefluorine-containing polymer having the functional group. It is morepreferable to use the fluorine-containing polymer having hydroxy groupat the end or side chain thereof, which is considered to easily cause antransesterification with an ester bond or carbonate bond in the mainchain of the aromatic polyester or polycarbonate.

[0098] A preferable concentration of the functional group differsdepending on the kind of the fluorine-containing polymer and the kindand ratio of the aromatic polyester or polycarbonate, and 2 to 2000μmol/g, particularly 2 to 1000 μmol/g is sufficiently effective per atotal weight of the fluorine-containing polymer having a functionalgroup.

[0099] When blending two components of the fluorine-containing resinhaving a functional group and the aromatic polyester or polycarbonate,various fluorine-containing resins having a functional group can beselected, and those having hydroxy group at the end or side chainthereof, such as PTFE, FEP, PFA, ETFE, ECTFE, PVdF, and VDF-TFEcopolymer are preferable. Mechanical properties and deflectiontemperature under load, which each of the correspondingfluorine-containing resins themselves has, can be improved.

[0100] In case of a blend composition by blending thefluorine-containing polymer having a functional group of the presentinvention as a compatibilizing agent with a blend of thefluorine-containing resin and the aromatic polyester or polycarbonate,various combinations can be used. Most preferable are those such as acomposition obtainable by blending a mixture of perfluorofluorine-containing resin (PTFE, FEP, PFA, and the like) and aromaticpolyester or polycarbonate, wherein each of the corresponding perfluorofluorine-containing resins, in which hydroxy group is introduced at theend or side chain thereof, is blended as a compatibilizing agent, acomposition obtainable by blending a mixture of a ETFE (or ECTFE) and anaromatic polyester or polycarbonate with ethylene/tetrafluoroethylenecopolymer (or ethylene/chlorotrifluoroethylene copolymer), in whichhydroxy group is introduced at the end or side chain thereof, and acomposition obtainable by blending a mixture of a PVDF and an aromaticpolyester or polycarbonate with a fluorine-containing polymer selectedfrom a PVDF or VDF copolymer, in which hydroxy group is introduced atthe end or side chain thereof.

[0101] In those cases, a content of the fluorine-containing polymerhaving a functional group, as a compatibilizing agent effective forenhancing a dispersibility, is 0.5 to 30% by weight, preferably 1 to 15%by weight per a total weight of the composition.

[0102] Also, by melting and blending an aromatic polyester withparticularly a fluorine-containing elastomer having hydroxy group, amongthe fluorine-containing polymers having a functional group, there occurspartially a chemical reaction (transesterification and the like), and athermoplastic elastomer composition can be obtained. Also, thermoplasticelastomers having various hardnesses can be obtained by melting andblending the fluorine-containing elastomer having hydroxy group and thearomatic polyester at an optionally selected blending ratio. Apreferable concentration of a functional group differs depending on thekinds, blending ratio, and the like of the fluorine-containing elastomerand the aromatic polyester or polycarbonate, but is 2 to 2000 μmol/g,particularly preferably 2 to 1000 μmol/g per total weight of thefluorine-containing elastomer.

[0103] In that case, as the fluorine-containing elastomer having hydroxygroup, there can be used a vinylidene fluoride-hexafluoropropylenecopolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylenecopolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer,vinylidene fluoride-tetrafluoroethylene-chlorotrifluoroethylenecopolymer, propylene-tetrafluoroethylene copolymer,tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,tetrafluoroethylene-vinyliden fluoride-propylene copolymer,ethylene-tetrafluoroethylene-hexafluoropropylene copolymer,ethylene-hexafluoropropylene copolymer, perfluoroalkyl acrylateelastomer, tetrafluoroethylene-alkylvinyl ether copolymer andtetrafluoroethylene-alkylvinyl ester copolymer, in which hydroxy groupis introduced at the end or side chain thereof. Among those,particularly preferable are vinylidene fluoride-hexafluoropropylenecopolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylenecopolymer and propylene-tetrafluoroethylene copolymer, in which hydroxygroup is introduced at the respective ends or side chains thereof.

[0104] In that thermoplastic elastomer composition, a weight ratio ofthe fluorine-containing elastomer having hydroxy group can be 50 to99.9% by weight, and that of the aromatic polyester or polycarbonate,0.1 to 50% by weight. In order to provide a high temperature flowabilityas the thermoplastic resin together with an elasticity as the elastomer,particularly preferable is 70 to 98% by weight of thefluorine-containing elastomer having hydroxy group and 2 to 30% byweight of the aromatic polyester or polycarbonate.

[0105] The modifying composition and the thermoplastic elastomercomposition of the fluorine-containing polymer mentioned hereinabove canbe used.

[0106] As the aromatic polyester, there are employed, for example, acondensate of dibasic acids such as adipic acid, terephthalic acid,2,6-naphthalene-dicarboxylic acid and 4,4′-biphenil carboxylic acid, anddihydric alcohols such as ethylene glycol, trimethylene glycol,tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,1,4-cyclohexanedimethanol and bisphenol A (for instance, polyethyleneterephthalate, polybutylene terephthalate, poly 1,4-cyclohexanedimethylene terephthalate, poly[2,2-propanebis(4-phenyltere/isophthalate)]) an aromatic polyester (liquid crystalcopolyester) forming an anisotropic melt phase, and the like.

[0107] Among those, it is preferable to use a liquid crystal copolyesterhaving a high strength because of an orientation thereof and showing ahigh flowability on melting. As the liquid crystal copolyesters, thereare employed those comprising, for example one or more of aromaticdicarboxylic acid and alicyclic dicarboxylic acid; one or more ofaromatic diol, alicyclic diol and aliphatic diol; one or more ofaromatic hydroxycarboxylic acids. Typical combinations are, forinstance, the one having main components of p-hydroxybenzoic acid,biphenildiol and terephthalic acid (for example, Econol E2000 and E6000available from Sumitomo Chemical Industries, Co., Ltd., Xydar RC/FC400and 300 available from Nippon Petrochemicals Co., Ltd., Vectra C seriesavailable from Polyplastics Co., Ltd., UENO LCP2000 available from UenoFine Chemicals Industry Ltd. and Idemitsu LCP300 available from IdemitsuPetrochemical Co., Ltd.); the one having main components ofp-hydroxybenzoic acid and 6-hydroxynaphthoic acid (for example, VICTREXSRP available from ICI Japan Ltd., UENO LCP1000 available from Ueno FineChemicals Industry Ltd., Vectra A series available from Mitsubishi KaseiCorp., Idemitsu LCP300 available from Idemitsu Petrochemical Co., Ltd.and Rodrun LC-5000 available from Unitika Ltd.); the one having maincomponents of p-hydroxybenzoic acid, terephthalic acid and aliphaticdiol (for example, Novaculate E310 available from Mitsubishi KaseiCorp., Idemitsu LCP100 available from Idemitsu Petrochemical Co., Ltd.,Rodrun LC-3000 of Unitika Ltd., and X7G available from Eastman KodakCo.).

[0108] When blending these liquid crystal copolyesters and thefluorine-containing elastomer having a functional group of the presentinvention, in consideration of thermal resistance of thefluorine-containing elastomer having a functional group, preferable arecopolyesters having a relatively low melting temperature, such as theone mainly comprising p-hydroxybenzoic acid and 6-hydroxynaphthoic acid,or the one mainly comprising p-hydroxybenzoic acid, terephthalic acidand aliphatic diol.

[0109] Polyamide resins are excellent in high strength, high toughnessand processability, and are widely used for hoses, tubes, pipes, and thelike. On the other hand, those resins, though being excellent generallyin oil resistance, are week against alcohol solvents. Particularly whengasolines containing low grade alcohol are used, oil resistance (gasoholresistance) deteriorates, and volumetric swelling and fuel permeabilityincrease, which causes deterioration of materials such as decrease instrength.

[0110] The solvent resistance and gasohol resistance of that polyamidecan be improved by blending the fluorine-containing polymer having afunctional group of the present invention with the polyamide and also byapplying, as a compatibilizing agent, the fluorine-containing polymerhaving a functional group to the blend of the fluorine-containingpolymer and the polyamide.

[0111] In that case, the both of hydroxy group and epoxy group(including glycidyl group) of the present invention can be used as thefunctional group of the fluorine-containing polymer. Particularlypreferable are the polymers having epoxy group (including glycidylgroup) at the end or the side chain thereof, because epoxy group isconsidered to have a good reactivity with the both of carboxyl group andamino group at the end of a polyamide resin.

[0112] When blending two components of the fluorine-containing polymerhaving a functional group and the polyamide, various polymers can beselected depending on the purpose and uses thereof, and particularlypreferable are ETFE, ECTFE, PVDE, VDF copolymer resins andfluorine-containing elastomer, of which respective ends or side chainshave a functional group.

[0113] Also, when blending three components, that is to say, thefluorine-containing polymer having a functional group of the presentinvention as a compatibilizing agent and a blend of afluorine-containing polymer and polyamide, various combinations can beused. The most preferable are a composition comprising a blend of a ETFE(or ECTFE) and a polyamide and, as a compatibilizing agent, anethylene/tetrafluoroethylene (or ethylene/chlorotrifluoroethylene)copolymer which has epoxy group (including glycidyl group) at the end orside chain thereof, a composition comprising a blend of a PVDF and apolyamide and, as a compatibilizing agent, a fluorine-containing polymerselected from a PVDF and a VDF copolymer, which has epoxy group(including glycidyl group) at the end or side chain thereof, and acomposition comprising a blend of a VDF copolymer and a polyamide resinand a fluorine-containing polymer selected from a PVDF and a VDFcopolymer, which has epoxy group (including glycidyl group) at the endor side chain thereof.

[0114] In that case, a content of the fluorine-containing polymer havinga functional group, which is effective for enhancing a dispersibility asa compatibilizing agent, is 0.5 to 30% by weight, preferably 2 to 15% byweight per a total amount of the composition.

[0115] As the polyamide resins of the present invention, there can beused nylon 6, nylon 6,6, nylon 11, nylon 12, nylon 610, nylon 46, nylonMCX-A, nylon MXD 6, and the like.

[0116] Further, the resin composition of the present invention maycontain fibrous reinforcements, for exmaple, glass fiber, carbon fiber,ceramic fiber, potassium titanate fiber and aramide fiber, inorganicfillers, for example, calcium carbonate, talc, mica, clay, carbonpowder, graphite, and glass beads, and inorganic or organic fillersusually used, for example, heat resisting resins such as polyimides,colorants and flame retarders within ranges not impairing the effect ofthe present invention. A content thereof is usually 1 to 70% by weightper the composition weight. At that time, there is a case where aneffect thereof is enhanced more because of the presence of a non-reactedfunctional group being contained in the resin composition of the presentinvention.

[0117] The present invention is explained further concretely by means ofthe following Reference Examples, Examples and Comparative Examples. Itis to be understood that the present invention is not limited to thescope.

[0118] The fluorine-containing polymers synthesized in the ReferenceExamples and the resin compositions obtained in Examples and ComparativeExamples were evalulated by the following test methods.

[0119] (Test Methods)

[0120] (1) Measurement of Thermal Resistance of the Fluorine-ContainingPolymer having a Functional Group

[0121] A temperature was measured at the time when the weight decreasedby 1% in nitrogen (30 ml/min.) at heat-up rate of 10° C./min. by the useof a heat analyzing unit DT-30 type of Shimazu Corporation.

[0122] (2) Izod Impact Test

[0123] An Izod notched impact strength was measured in accordance withASTM D256 by the use of a U-F impact tester of Ueshima Seisakusho Ltd.

[0124] (3) Electronmicroscopic Observation

[0125] A molded article of a resin composition was frozen and broken inliquid nitrogen, and the section thereof was observed by a scanning typeelectron microscope. Further, a hundred of the fluorine-containingpolymer particles were optionally selected from the microscopicphotograph (150 μm×200 μm), and an average particle size was obtainedtherefrom.

[0126] (4) Tension Test

[0127] A tensile strength was measured in accordance with ASTM D638 bythe use of a Tensilon universal tester of Orientec Corporation and atype 5 dumbbell.

[0128] (5) Melt Flow Rate

[0129] A melt flow rate was measured at a temperature of 250° C. and aload of 20 kgf/cm² for 300 seconds of preheating by the use of a flowtester of Shimazu Corporation.

[0130] (6) Deflection Temperature Under Load

[0131] Measurement was made under the conditions of a load of 18.5kgf/cm² and thermal up rate of 2° C./min. in N₂ stream by the use of athermal distortion tester (No. 148 HD-500-PC type) of Yasuda SeikiSeisakusho Ltd.

[0132] (7) Solvent Resistance

[0133] A volume change was measured by the use of a mixed solvent oftoluene/isooctane/methanol at 40/40/20% by volume respectively inaccordance with JIS-K630 after 70 hr dipping at 100° C.

REFERENCE EXAMPLE 1

[0134] By the method disclosed in Example 3 (1) of JP-B-49327/1986,there was obtained a white aqueous latex which contained 25% by weightof solids of 50/20/30% by mole of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene copolymer which wasprovided with iodine at the end thereof by a method with a chaintransfer agent. A part of that latex was frozen, coagulated, rinsed anddried, thus an achromatic transparent elastomer was obtained. Anumber-average molecular weight of that polymer, which was obtained byGPC analysis (solvent: THF, column temperature: 40° C.), was about 140thousands by a conversion with polystyrene, and an iodine content by anelement analysis was 0.22% by weight. Also, thermal resistance of thatpolymer was 401° C.

[0135] A 2000 ml four neck flask equipped with an agitator, coolingtube, thermometer and nitrogen blowing tube was charged with 1000 g ofthat latex and 4.2 g of allyl alcohol, and was then heated to 70° C. ona water bath, being agitated under a nitrogen stream at a flow rate ofabout 0.2 ml/min. 10 ml of an aqueous solution, in which 20 mg ofammonium persulfate had been melted, was added in the flask, and areaction was started. After a lapse of seven hours, heating andagitation were stopped for cooling. After having been frozen andcoagulated, the latex was rinsed and dried, and an achromatictransparent elastomer was obtained. Subsequently a 2000 ml four neckflask equipped with an agitator, cooling tube and thermometer wascharged with 250 g of that elastomer and 1 liter of ethyl acetate, andheating and agitation were carried out to melt the polymer. With a flaskinner temperature being kept at 70° C., 200 g of an aqueous solutionhaving 10% by weight of potassium hydroxide was added, and the reactionwas done for seven hours. The reacted solution was poured into a largeamount of methanol to re-precipitate and recover the polymer which wasthen rinsed and dried. A content of iodine at the end thereof was 0.14%by weight by an element analysis, and the epoxidation ratio obtained byan iodine amount having decreased by the epoxidation reaction was 36%.Also, thermal resistance of the polymer was 356° C., and the glasstransition point was −9° C. The concentration of epoxy group containedin that polymer was calculated with a number-average molecular weight,that is, 5 μmol/g.

REFERENCE EXAMPLE 2

[0136] A 1-liter pressure vessel equipped with an agitator was chargedwith 500 g of the latex of the iodine terminated fluorine-containingelastomer synthesized in Reference Example 1, and after substituting theinner gas sufficiently with nitrogen gas, the vessel pressure wasincreased to 0.8 MPa by ethylene gas with the vessel temperature beingkept at 70° C. under the agitation. By forcedly charging 50 mg of APS,immediately a pressure drop started. At the stage where a pressure dropwas no longer found after a lapse of 14 hours, the vessel temperaturewas lowered to room temperature, and the remaining pressure wasdischarged to complete the reaction. After freezing and coagulating ofthe resulting latex, rinsing and drying were carried out to obtain anachromatic transparent elastomer. In the infrared absorption spectrum ofthat polymer, there was recognized a characteristic absorption of CHbond of ethylene introduced in the end iodine, at 3024 cm⁻¹.

[0137] Then a 1000 ml four neck flask equipped with an agitator, coolingtube, thermometer and nitrogen blowing tube was charged with 68 g ofthat elastomer, 3.0 g of dimethyl sulfoxide, 400 g of butyl acetate and2 g of water, and were heated up to 110° C., being agitated under anitrogen gas stream at a rate of about 0.2 ml/min. After a lapse of fivehours, heating and agitation were stopped, and the yellow-coloredpolymer solution was obtained That solution was poured into a largeamount of methanol to recover the polymer. Afterwards rinsing and dryingwere repeated in the methanol to obtain light yellowish elastomer. Inthe infrared absorption spectrum of that polymer, there was recognized acharacteristic absorption of hydroxy group caused by the end reaction,at 3400 cm⁻¹.

[0138] The content of the end iodine by an element analysis was 0.10% byweight, and the hydroxylation ratio obtained by the iodine amount havingdecreased by the hydroxylation reaction was 55%. Also, thermalresistance of that polymer was 453° C., and the glass transition pointwas −9° C. The concentration of hydroxy group contained in that polymerwas calculated by a number-average molecular weight, that is, 8 μmol/g.

REFERENCE EXAMPLE 3

[0139] A 3-liter stainless autoclave equipped with a stainless agitationblade and a jacket for temperature control was charged with 1425 ml ofdeionized water and 0.75 g of emulsifier (ammonium perfluorooctanoate),and oxygen in a system was substituted with a nitrogen gas three timesto discharge oxygen therefrom. Then the autoclave was charged with 8.1 gof CF₂═CFCF₂CH₂OH, and 78 g of a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1 of mole ratio)mixture monomer was forcedly charged. By keeping the agitator at 400 rpmand the inner temperature at 40° C., the inner pressure became 1.2 MPa.Then an aqueous ammonium persulfate solution (6 g/25 ml), aqueous sodiumsulfite solution (3.18 g/25 ml), and aqueous ferric sulfate solution(3.66 g/25 ml) were forcedly charged in order with the mixture monomer.During the reaction, the mixture monomer was continuously supplied tokeep the temperature at 40° C., the agitation of 400 rpm and the innerpressure of 1.1 MPa. Also, an ammonium persulfate amounting to a half ofthat supplied at the time of starting the reaction was additionallysupplied four hours later.

[0140] When the amount of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio)mixture monomer consumption for the reaction had reached 400 g afteraddition of initiators (about 15 hours later), the agitation and supplyof the mixture monomer were stopped immediately, and gases remaining inthe autoclave were discharged until normal pressure was reached, and thereaction completed. The obtained fluorine-containing copolymer wasrinsed and dried under the reduced pressure at 70° C. for 24 hours. Theresulting dried powder was 430 g in total.

[0141] An absorption peak reverted to hydroxy group of CF₂═CFCF₂CH₂OHwas recognized at 3420 cm⁻¹ of the infrared absorption spectrum of thefilm obtained by compression-molding of the dried powder. The elementanalysis and the 19F nuclear magnetic resonance analysis (NMR) indicatethat the fluorine-containing polymer comprised a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene/CF₂═CFCF₂CH₂OH(57.4/25.6/16.8/0.2). A number-average molecular weight of that polymer,which was obtained by GPC analysis (solvent: THF, column temperature:40°C.), was about 60 thousands by a conversion with polystyrene. Also,thermal resistance of that polymer was 401° C., and the glass transitionpoint was −18° C. The concentration of the hydroxy group contained inthe polymer is calculated to be 18 μmol/g.

REFERENCE EXAMPLE 4

[0142] A 3-liter stainless autoclave equipped with a stainless agitationblade and a jacket for temperature control was charged with 1425 ml ofdeionized water and 0.75 g of emulsifier (ammonium perfluorooctanoate),and oxygen in the system was substituted with a nitrogen gas three timesto discharge oxygen therefrom. Then the autoclave was charged with 3 gof CF₂═CFCF₂CH₂OH, and 78 g of a mixture monomer of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio) wasforcedly charged therein By keeping an agitation at 400 rpm and an innertemperature at 40° C., the inner pressure became 1.2 MPa Subsequently anaqueous ammonium persulfate solution (6 g/25 ml), aqueous sodium sulfitesolution (3.18 g/25 ml), and aqueous ferric sulfate solution (3.66 g/25ml) were forcedly charged in order with the mixture monomer. During thereaction, the temperature was kept at 40° C. and the agitation, at 400rpm. The mixture monomer was continuously supplied to keep the innerpressure at 1.1 MPa. Also, the ammonium persulfate was additionallycontinuously supplied in a total amount of 3 g for ten hours from thestart of the reaction.

[0143] When the amount of the mixture monomer of vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (3/1/1, mole ratio),which had been consumed by the reaction after addition of initiators,reached 400 g (after a lapse of about 22 hours), the agitation andsupply of the mixture monomer were immediately stopped, and gasesremaining in the autoclave were discharged until the normal pressure wasreached, and the reaction was completed. The obtainedfluorine-containing copolymer was coagulated and rinsed, and then driedat 70° C. for 24 hours under the normal pressure. The resulting driedpowder was 380 g in total.

[0144] The element analysis and ¹H, ¹⁹F nuclear magnetic resonanceanalysis (NMR) indicate that the fluorine-containing polymer comprised avinylidenfluoride/tetrafluoroethylene/hexafluoropropylene/CF₂═CFCF₂CH₂OH(62.8/23.8/13.3/0.08, mole ratio). A number-average molecular weight ofthe polymer, which was obtained by GPC analysis (solvent: THF, columntemperature: 40° C.), was about 210 thousands by a conversion withpolystyrene. Thermal resistance of that polymer was 445° C., and theglass transition point was −19° C. The concentration of OH groupcontained in the polymer is calculated to be 12 μmol/g.

REFERENCE EXAMPLE 5

[0145] In accordance with the method disclosed in JP-A-12734/1987, awhite aqueous latex having 21% by weight of solids of a vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene/CF₂═CFOCF₂ CF₂ CH₂1(49.7/19.9/29.8/0.6, mole ratio) copolymer was obtained. Aftercoagulated, that latex was rinsed and dried to obtain an achromatictransparent elastomer. A number-average molecular weight of the polymer,which was measured by GPC analysis (solvent: THF, column temperature:40° C.), was about 140 thousands by a conversion with polystyrene. Theiodine content measured by an element analysis was 0.72% by weight.Also, thermal resistance of that polymer was 403° C.

[0146] A 6-liter autoclave made of glass, which was equipped with aglass lining agitation blade and a jacket for temperature control, wascharged with 3300 g of that latex, and after oxygen in the system wassubstituted with a nitrogen gas three times, the inner pressure wasincreased up to 0.9 Mpa with an ethylene gas with the agitation andinner temperature being kept at 305 rpm and 70° C. respectively.Subsequently an aqueous ammonium persulfate solution (30 mg/2 ml) wasforcedly charged with a nitrogen gas. During the reaction, thetemperature was kept at 70° C., and the agitation, at 305 rpm.

[0147] When a pressure drop was no longer found (after a lapse of about13.5 hours), gases remaining in the autoclave were discharged until thenormal pressure was reached, and the reaction was completed. Theobtained fluorine-containing copolymer was coagulated and rinsed, andthen dried at 80° C. for 48 hours under the normal pressure. Thus theachromatic transparent elastomer was obtained. The resulting driedpolymer was 690 g in total.

[0148] By ¹H nuclear magnetic resonance analysis (NMR), it was confirmedthat a peak of 4.0 ppm resulting from —CF₂CH₂I bond had disappeared andethylene had been added. An element analysis indicates 0.57% by weightof iodine, and a number-average molecular weight of the polymer, whichwas measured by GPC analysis (solvent: THF, column temperature: 40° C.),was about 140 thousands by a conversion with polystyrene. Also, thermalresistance of that polymer was 427° C.

[0149] A 1000 ml four neck flask equipped with an agitator, coolingtube, thermometer and nitrogen gas blowing tube was charged with 100 gof ethylene-added iodine-terminated fluorine-containing elastomer, 400 gof dimethyl sulfoxide (DMSO) and 2 g of water, and was heated to 100°C., being agitated under bubbling with nitrogen gas blown at a rate ofabout 0.2 ml/min. Five hours later, heating and agitating were stopped,and a yellow-colored polymer was obtained. That polymer was melted inacetone to obtain a yellow-colored polymer solution. That solution waspoured in a large amount of methanol for recovering the polymer whichwas then, after further rinsing, dried at 100° C. for 24 hours undernormal pressure, and a light yellow polymer was obtained.

[0150] The iodine content by an element analysis was 0.11% by weight.The hydroxylation ratio calculated by an iodine amount having decreasedby the hydroxylation reaction was 80.7%. The thermal resistance of thatpolymer was 452° C. The concentration of hydroxy group contained in thatpolymer is calculated by the number-average molecular weight to be 57μmol/g.

EXAMPLE 1

[0151] A 60 cm³ Brabender mixer set at 300° C. was filled with 50.4 g ofpolyphenylene sulfide (Tohpren T4 of Tohpren Co., Ltd.), and melting wascarried out for four minutes at 50 rpm. Then 7.6 g of the polymerobtained in Reference Example 1 was added, and then kneaded for sixminutes at 100 rpm. In that csae, the degree of the torque increaseduring kneading was larger than that of Comparative Example 1 asdescribed hereinafter. The obtained composition was compression-moldedat 300° C., and a test piece was made. The test results are shown inTable 1.

EXAMPLES 2, 3 AND 4

[0152] 44.8 G of a polyphenylene sulfide resin was kneaded and molded inthe same manner as in Example 1, with the use of 15.2 g each of thepolymers obtained in Reference Examples 1, 2 and 3, and a test piece wasmade. The test results are shown in Table 1.

EXAMPLE 5

[0153] 44.8 G of a polyphenylene sulfide resin, 3.2 g of the polymerobtained in Reference Example 1 and 15.2 g of a fluorine-containingelastomer (Daiel G701 of Daikin Industries, Ltd.) comprising avinylidene fluoride/hexafluoropropylene copolymer were kneaded andmolded in the same manner as in Example 1, and a test piece was made.The test results are shown in Table 1.

COMPARATIVE EXAMPLE 1

[0154] 44.8 G of a polyphenylene sulfide resin and 15.2 g of afluorine-containing elastomer (Daiel G701 of Daikin Industries, Ltd.)comprising a vinylidene fluoride/hexafluoropropylene copolymer werekneaded and molded in the same manner as in Example 1, and a test piecewas made. The test results are shown in Table 1.

COMPARATIVE EXAMPLE 2

[0155] A 60 cm³ Brabender mixer set at 300° C. was filled with 60 g of apolyphenylene sulfide resin, and melting was carried out at 500 rpm forfour minutes, and further melting was done at 100 rpm for six minutes.Then a test piece was made in the same manner as in Example 1. The testresults are shown in Table 1. TABLE 1 Examples Comparative Examples 1 23 4 5 1 2 Components (% by weight) Fluorine-containing polymer (a)having a functional group Reference Example 1 4.7 9 — — 1.8 — —Reference Example 2 — — 13.8 — — — — Reference Example 3 — — — 25 — — —Thermoplastic resin (b) 87 75 75 75 71 75 100 Others 8.3⁽¹⁾ 16⁽¹⁾11.2⁽¹⁾ — 27.2⁽²⁾ 25⁽³⁾ — Properties of molded article Izod impactstrength (kgcm/cm) 1.7 2.1 4.2 4.5 1.7 1.5 1.4 Average dispersionparticle 3 4 1 2 5 9 — size (μm)

[0156]FIGS. 1, 2, 3 and 4 are microscopic photographs (×500)respectively showing the cut surfaces of the molded articles obtained inExample 2 and 3 and Comparative Examples 1 and 2.

[0157] As is clear from FIGS. 1 to 4, a dispersibility of afluorine-containing elastomer of a blend of the fluorine-containingelastomer (Reference Examples 1 and 2), in which a functional group isintroduced, with a polyphenylene sulfide (Example 2—FIG. 1, and Example3—FIG. 2 respectively) is better than the case (Comparative Example—FIG.3) where the conventional fluorine-containing elastomer is blended. Thusit can be observed that the improvement of mechanical property (Izodimpact strength) are effectively done.

EXAMPLE 6

[0158] A 60 cm³ Brabender mixer set at 200° C. was filled with 8.3 g ofliquid crystal copolyester (Novaculate E310 of Mitsubishi Kasei Corp.)which was melted at 10 rpm for 1.5 minutes. Then 73.8 g of the polymerobtained in Reference Example 3 was added at 50 rpm, and was kneaded at100 rpm for five minutes. The obtained composition wascompression-molded at 200° C., and a test piece was made. The testresults are shown in Table 2.

EXAMPLE 7

[0159] 8.3 G of liquid crystal copolyester (Novaculate E310) was kneadedwith 73.8 g of the polymer obtained in Reference Example 4 and molded inthe same manner as in Example 6, and a test piece was made. The testresults are shown in Table 2.

EXAMPLE 8

[0160] 8.3 G of liquid crystal copolyester (Novaculate E310) was kneadedwith 73.9 g of the polymer obtained in Reference Example 5 and molded inthe same manner as in Example 6, and a test piece was made. The testresults are shown in Table 2.

COMPARATIVE EXAMPLE 3

[0161] 420 G of a fluorine-containing polymer having no functional groupwas obtained in the same manner as in Reference Example 3 except thatCF₂═CFCF₂CH₂OH was not used.

[0162] The components of the fluorine-containing polymer, which wasobtained by an element analysis and ¹H, ¹⁹F nuclear magnetic resonanceanalysis (NMR), was vinylidenefluoride/tetrafluoroethylene/hexafluoropropylene (61.3/18.9/19.8, moleratio). A number-average molecular weight of that polymer was calculatedby GPC analysis (solvent: THF, column temperature: 40° C.) to be about210 thousands by a conversion with polystyrene. The thermal resistanceof that polymer was 456° C., and the glass transition point was −17° C.

[0163] 73.8 G of that fluorine-containing polymer having no functionalgroup was kneaded with 8.3 g of liquid crystal copolyester (NovaculateE310) and molded, and then a test piece was made in the same manner asin Example 6. The test results are shown in Table 2.

COMPARATIVE EXAMPLE 4

[0164] 73.9 G of the fluorine-containing elastomer which was prepared bycoagulating, rinsing and drying a latex synthesized in Reference Example5 prior to addition of ethylene thereto, was kneaded with 8.2 g ofliquid crystal copolyester (Novaculate E310) and molded, and then a testpiece was made in the same manner as in Example 6. The test results areshown in Table 2. TABLE 2 Comparative Examples Examples 6 7 8 3 4Components (% by weight) Fluorine-containing polymer (a) having afunctional group Reference Example 3 90 — — — — Reference Example 4 — 90— — — Reference Example 5 — — 72.6 — — Thermoplastic resin (b) 10 10 1010 10 Others — — 17.4⁽¹⁾ 90⁽²⁾ 90⁽³⁾ Properties of molded articleMaximum tensile strength 186 146 29.7 9.0 5.6 (kgf/cm²) Melt flow rate(g/l0 min) 74.4 59.3 7.3 108 119

[0165]FIG. 5 shows a stress-strain curve obtained in Reference Examples6, 7, 8 and Comparative Examples 3 and 4.

[0166] As is clear from Table 2 and FIG. 5, a blend (same as those ofReference Examples 6, 7 and 8) of a fluorine-containing elastomer(synthesized in Reference Examples 3, 4 and 5), in which a functionalgroup was introduced, and a liquid crystal copolyester shows a highstress against the elongation and has crosslinking rubber like physicalproperties. Also the blend of the functional group-introducedfluorine-containing elastomer and the liquid crystal copolyester shows ahigh temperature flowability, and therefore has thermoplasticelastomeric properties. Because a blend (same as those of ComparativeExamples 3 and 4) with a fluorine-containing elastomer having nofunctional group is a mere blend of a non-vulcanized rubber and a liquidcrystal copolyester, and therefore has a flowability at high temperaturebut shows only a low stress against an elongation.

EXAMPLE 9

[0167] 8.0 G of a polycarbonate (Panlite L1225WP available from TeijinChemicals Ltd.) and 72.4 g of the polymer obtained in Reference Example4 were kneaded in the Brabender mixer set at 285° C. in the same manneras in Example 6. The obtained composition was compression-molded at 285°C., and a test piece was made. The test results are shown in Table 3.

EXAMPLE 10

[0168] 8.1 G of polybutyrene terephthalate (Valox 310 available from GEPlastics Japan Ltd.) and 73.3 g of the polymer obtained in ReferenceExample 4 were kneaded in the Brabender mixer set at 240° C. in the samemanner as in Example 6. The obtained composition was compression-moldedat 240° C., and a test piece was made. The test results are shown inTable 3.

COMPARATIVE Example 5

[0169] Kneading and molding were carried out by the use of afluorine-containing polymer having no functional group as shown inComparative Example 3 in the same manner as in Example 9, and a testpiece was made. The test results are shown in Table 3.

COMPARATIVE EXAMPLE 6

[0170] Kneading and molding were carried out by the use of afluorine-containing polymer having no functional group as shown inCompartive Example 3 in the same manner as in Example 10, and a testpiece was obtained. The test results are shown in Table 3. TABLE 3Examples Comparative Examples 9 10 5 6 Components (% by weight)Fluorine-containing elastomer (a) 90 90 — — having a functional group(Synthesized in Reference Example 4) Thermoplastic resin (b) 10 — 10 —Polycarbonate Polybutyrene terephthalate — 10 — 10 Fluorine-containingelastomer (1) — — 90 90 having no functional group Properties of moldedarticle Maximum tensile strength (kgf/cm²) 163 119 10.7 10.4 Elongationat break (%) 695 647 — — Melt flow rate (g/10 min) 4.9 130 110 102(Measured (Measured (Measured (Measured at 300° C.) at 290° C.) at 300°C.) at 290° C.)

[0171] When blending a fluorine-containing elastomer (synthesized inReference Example 4) with a polycarbonate (Example 9) and alsopolybutyrene terephthalate (Example 10), the resulting blend shows astrong stress against an elongation, and further shows a hightemperature flowability, which represents thermoplastic elastomericproperties. Contrary to that, the compositions of Comparative Examples 5and 6 show only a low stress against an elongation like non-vulcanizedrubbers.

EXAMPLE 11

[0172] There were uniformly blended a PVDF (Neoflon VDF VP-800 availablefrom Daikin Industries, Ltd.), a liquid crystal polyester (VectraA950-non-reinforced available from Polyplastic Co., Ltd.) and afluorine-containing polymer having a functional group as shown inReference Example 4, in a weight ratio shown in Table 4. Then kneadingand extruding were carried out at 280° to 300° C. by a twin screwextruder to make pellets. By the use of those pelletes, test pieces weremade at a cylinder temperature of 240° to 290° C. and a mold temperatureof 50° C. by an injection molding machine. The test results are shown inTable 4.

COMPARATIVE EXAMPLE 7

[0173] By the use of a PVDF (same as that of Example 11) and a liquidcrystal polyester (same as that of Example 11), kneading and extrudingwere carried out in the same manner as in Example 11, and a test piecewas made by an injection molding. The test results are shown in Table 4.

EXAMPLE 8

[0174] The pellets of the PVDF (same as that of Example 11) wereinjection-molded under the same conditions as in Example 11, and a testpiece was obtained. The test results are shown in Table 4. TABLE 4Comparative Example Examples Components (% by weight) 11 7 8Fluorine-containing polymer (a) 3 — — having a functional groupReference Example 4 Thermoplastic resin (b) 20 20 — Liquid crystalpolyester Others 77 80 100 PVDF resin Deflection temperature 146 130 101under load (° C.)

[0175] It is known from Table 4 that the deflection temperature underload can be further improved to a large extent by adding thefluorine-containing polymer having a functional group (the onesynthesized in Reference Example 4) when blending thefluorine-containing resin and the liquid crystal polyester, as comparedwith the blend (Comparative Example 7) of only a fluorine-containingresin and a liquid crystal polymer.

EXAMPLE 12

[0176] A 60 cm³ Brabender mixer set at 190° C. was charged with 40.4 gof polyamide 12 (Rilsan AMNφ available from Toray Industries, Inc.)which was then melted at 10 rpm for 1.5 minutes. 10.1 g of the polymerobtained in Reference Example 1 was added at 50 rpm and was kneaded at80 rpm for 7 minutes. The obtained composition was compression-molded at200° C., and a test piece was made. The test results are shown in Table5.

EXAMPLE 13

[0177] A 60 cm³ Brabender mixer set at 190° C. was charged with 40.2 gof polyamide 12 (same as that of Example 12) and 13.4 g of PVDF (same asthat of Example 11), and melting was carried out at 10 rpm for twominutes. 2.5 G of the polymer obtained in Reference Example 1 was addedat 50 rpm, and kneaded at 80 rpm for seven minutes. The obtainedcomposition was compression-molded at 200° C., and a test piece wasmade. The test results are shown in Table 5.

COMPARATIVE EXAMPLE 9

[0178] Kneading and molding were carried out in the same manner as inExample 12 except that the fluorine-containing elastomer (Daiel G902available from Daikin Industries, Ltd.) was used instead of thefluorine-containing polymer having functional group obtained inReference Example 1, and a test piece was made. The test results areshown in Table 5.

COMPARATIVE EXAMPLE 10

[0179] A 60 cm³ Brabender mixer set at 190° C. was charged with 40.1 gof polyamide 12 (same as that of Example 12) and 10.0 g of PVdF (same asthat of Example 11), and kneading was carried out at 10 rpm for twominutes and further at 80 rpm for seven minutes. The obtainedcomposition was compression-molded at 200° C., and a test piece wasmade. The test results are shown in Table 5.

COMPARATIVE EXAMPLE 11

[0180] The pellets of polyamide 12 (same as that of Example 12) wascompression-molded, and a test piece was made. The test results areshown in Table 5. TABLE 5 Comparative Examples Examples Components (% byweight) 12 13 9 10 11 Fluorine-containing elastomer (a) 20 5 — — —having a functional group (Synthesized in Reference Example 1)Thermoplastic resin (b) 80 80 80 80 100 Polyamide Others PVDF — 15 — 20— Fluorine-containing elastomer (1) — — 20 — — Solvent resistance test18 16 27 23 30 Volume change (%) Izod impact strength (kgcm/cm) 3.8 —2.0 — 1.8 Average dispersion particle size (μm) 1 — 6 — —

[0181] As is clear from Table 5, the blend (same as that of Example 12)of a fluorine-containing polymer having a functional group and apolyamide and the blend (same as that of Example 13) of afluorine-containing polymer having a functional group and a mixture of aPVDF and polyamide shows a good effect on the improvement in chemicalresistance (gasohol resistance).

[0182]FIGS. 6 and 7 show microscopic photographs (×5000) of cut surfacesof the molded articles obtained in Example 12 and Comparative Example 9,respectively.

[0183] As is clear by comparing FIG. 6 with 7, the blend (same as thatof Example 12) of a fluorine-containing polymer (synthesized inReference Example 1) having a functional group and a polyamide shows agood dispersibility of the fluorine-containing polymer as compared withthe blend (same as that of Comparative Example 9) of afluorine-containing polymer having no functional group and a polyamide.It is observed that mechanical properties (Izod impact strength) areeffectively carried out.

[0184] By introducing a functional group in a fluorine-containingpolymer, an interfacial affinity of the resin composition of the presentinvention is improved, and the resin composition is presented as thematerials suitable for various functional parts, having excellentmechanical properties and moldability of the thermoplastic resintogether with excellent chemical resistance and impact resitance of thefluorine-containing polymer.

INDUSTRIAL APPLICABILITY

[0185] In the present invention, the fluorine-containing polymer (a)having a functional group is blended with the thermoplastic resin (b) ofa crystalline melting point or glass transition temperature of not lessthan 150° C. As thermoplastic resins, there are, for example,polyacetals, polyamides, polycarbonates, polyphenylene ethers, aromaticpolyesters, aromatic polyesteramides, aromatic azomethines, polyallylenesulfides, polysulphones and polyether sulfones, polyketones andpolyether ketones, polyetherimides, polyamide imides,polymethylpentenes, polyether nitrites and also polymer alloy mainlycomprising those resins. Among those, preferable for the presentinvention are such resins, for which general modifiers for impactresistance and chemical resistance cannot be used because ofinsufficient thermal resistance as a melting and kneading temperature isnot less than 200° C. As such resins, there are aromatic polyesters,polyamides, polyamide imides, polyallylene sulfides, polyketones,polyether nitrites, polycarbonates, polyphenylene ethers, polysulphones,polyether imides, and polyimides.

What is claimed is:
 1. A thermoplastic resin composition which comprisesa blend obtainable by blending 0.1 to 99% by weight of (a) afluorine-containing polymer having a functional group and anumber-average molecular weight of 2000 to 1000000 and 1 to 99.9% byweight of (b) a heat resisting thermoplastic resin having a crystallinemelting point or glass transition temperature of not less than 150° C.;said fluorine-containing polymer (a) having the functional group is atleast one selected from fluorine-containing polymers having functionalgroups, in which a concentration of the functional groups at a mainchain end portion and side chain portion is 2 to 2000 μmol/g per thetotal weight of the fluorine-containing polymer, and represented by theformula [I], A^(XYA) ²  [I]wherein X is a structural unit of theformula CH₂CX¹X² (wherein X¹ and X² are the same or different, andeach is hydrogen atom, fluorine atom, CH₂_(p)O_(q)R—B¹ (R is adihydric hydrocarbon group having carbon atoms of 1 to 20 or dihydricfluorine-substituted organic group having carbon atoms of 1 to 20, B¹ ishydrogen atom, fluorine atom, hydroxy group or epoxy group, p is 0 or 1and q is 0 or 1), —OCO—R—B¹ (R and B¹ are the same as above) or—COO—R—B¹ (R and B¹ are the same as above)); Y is a structural unit ofthe formula CF₂CY¹Y² (wherein Y¹ and Y² are the same or different, andeach is hydrogen atom, fluorine atom, chlorine atom,CF₂_(r)O_(s)R_(f)_(t)CH₂_(u)B² (R_(f) is a dihydricfluorine-substituted organic group having carbon atoms of 1 to 14, B² ishydrogen atom, halogen atom, hydroxy group, epoxy group or glycidyloxygroup, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is an integer of 1to 3) or CF₂_(v)B³ (B³ is hydrogen atom, fluorine atom or chlorineatom, v is an integer of 1 to 10)); both A¹ and A² are end portions of amain chain; provided that each of X and Y may comprise two or morestructural units; Y may not be present when X has the structural unitderived from CH₂═CHF, CH₂═CF₂ or fluoroalkyl-α-substituted acrylate(substituent is hydrogen atom, fluorine atom or methyl); X may not bepresent when Y has the structural unit derived from CF₂═CF₂ or CF₂═CHC1;at least one of A¹ and A² contains hydroxy group, epoxy group orglycidyl group when both of X and Y do not contain hydroxy group, epoxygroup or glycidyl group.
 2. The composition of claim 1, wherein the heatresisting thermoplastic resin (b) is a polyallylene sulfide.
 3. Thecomposition of claim 1, wherein the fluorine-containing polymer (a)having the functional group is an elastomer having a number-averagemolecular weight of 2000 to 200000, the heat resisting thermoplasticresin (b) is a polyallylene sulfide, and a ratio of (a)/(b) is 0.1 to40% by weight/99.9 to 60% by weight.
 4. The composition of claim 1,wherein the heat resisting thermoplastic resin (b) is a polyamide. 5.The composition of claim 1, wherein the heat resisting thermoplasticresin (b) is an aromatic polyester.
 6. The composition of claim 5,wherein the aromatic polyester is a liquid crystal polyester having ananisotropy on melting.
 7. The composition of claim 1, wherein thefluorine-containing polymer (a) having a functional group is afluorine-containing elastomer having hydroxy group, the heat resistingthermoplastic resin (b) is a liquid crystal polyester having ananisotropy on melting, and a weight ratio of (a)/(b) is 50 to 99.9/0.1to 50.